Process for the production of synthesis gas by oxidative converson of methane (or natural gas) using composite catalyst containing transitional and alkine earth metal oxides

ABSTRACT

The invention relates to a process for the production of synthesis gas by oxidative conversion of methane using composite catalysts having the formula: T m  AO n , wherein T is a transition metal or metals, m is the T/A mole ratio and is from 0.01 to 100, A is an alkaline earth metal or metals, O is oxygen and n is the number of oxygen atoms needed to form a catalyst composite wherein each element of the composite has a complete set of valence electrons. In a preferred embodiment, the process includes passing a gas containing methane and oxygen over the composite catalyst in a fixed bed reactor at a pressure in the range of 0.5-50 atm, and at a temperature in the range of 200°-1000° C., and recovering the synthesis gas.

This invention relates to an improved process for the production of synthesis gas (i.e. CO and H₂) by oxidation conversion of methane (or natural gas) using composite catalysts containing transitional and alkaline earth metal oxides. The process of this invention is useful for the production of synthesis gas (i.e. CO and H₂) and also CO or H₂ from methane or natural gas. The process of the present invention could be used by the producers of synthesis gas, CO and H₂, as well as by users of synthesis gas, CO and H₂ ; for example, those producing methanol and methanol based products, Fischer-Tropsch synthesis products such as olefins, liquid hydrocarbons, alcohols and aldehydes, oxo-synthesis products, ammonia and ammonia based fertilizers and chemicals, town gas and also reduction gas used for the production of sponge iron, etc.

The conversion of methane or natural gas to synthesis gas or carbon monoxide (CO) and hydrogen (H₂) by catalytic steam reforming, autothermal catalytic reforming and non-catalytic partial oxidation, is known in the prior art.

The catalytic steam reforming of methane or natural gas to synthesis gas (i.e. hydrogen and carbon monoxide) is a well established technology practiced for commercial production of hydrogen, carbon monoxide and syngas (i.e. mixture of hydrogen and carbon monoxide). In this process, hydrocarbon feeds are converted to a mixture of H₂, CO and CO₂ by reacting hydrocarbons with steam over a catalyst (NiO supported on calcium aluminate, alumina, spinel type magnesium aluminum oxide or calcium aluminate titanate) at elevated temperature (850°-1000° C.) and pressure (10-40 atm) and at steam/carbon mole ratio of 2-5 and gas hourly space velocity (based on wet feed) of about 5000-8000 per hour. This process involved following reactions.

    CH.sub.4 +H.sub.2 O⃡CO+3H.sub.2.

    or

    C.sub.n H.sub.m +nH.sub.2 O⃡nCO+[n+(m/2)]H.sub.2.

    and

    CO+H.sub.2 O⃡CO.sub.2 +H.sub.2 (shift reaction).

The conversion is highly endothermic and is carried out in a number of parallel tubes packed with catalyst and externally heated by flue gas of temperature of 980°-1040° C. (Kirk and Othmer, Encyclopedia of Chemical Technology, 3rd Edn., 1990 vol. 12 p. 951; Ullamann's Encyclopedia of Industrial Chemistry, 5th Edn., 1989, vol. A-12 p. 186). The main drawbacks of this process are as follows. It is highly endothermic and operated at high temperature. Hence, it is highly energy intensive. Further, the shift reaction occurring in the process energy intensive. Further, the shift reaction occurring in the process leads to formation of CO₂ and H₂ from CO and water, thus increasing H₂ /CO ratio. Since lower H₂ /CO ratio than that obtained by the steam reforming is required for certain applications of synthesis gas, secondary reformers using CO₂ or O₂ oxidants are frequently required to reduce the hydrogen content of synthesis gas produced by the steam reforming. Also, the supported nickel catalyst used in the steam reforming is poisoned by sulfur containing compounds present in very low concentrations in the feed hydrocarbons. Further, there is a carbon deposition on the catalyst during the steam reforming.

Autothermal catalytic reforming of methane or natural gas with air or oxygen to H₂, CO and CO₂ is also a established technology. In this process, a feed gas mixture containing hydrocarbon, steam and oxygen (or air) is passed through a burner and then the combustion gases are passed over a catalyst (nickel supported on alumina) in a fixed bed reactor at 850°-1000° C. and 20-40 atm. (Ullamann's Encyclopedia of Industrial Chemistry 5th Edn., 1989, vol. A 12, p. 202). This process has the following drawbacks. There are large temperature and space velocity variations during start-up and shut down which leads to abrasion and catalyst disintegration, requiring frequent refilling and removal of the catalyst. This process operates at high temperature and pressure and there is a formation of carbon (or carbon deposition) in the reactor.

Non-catalytic partial oxidation of hydrocarbons to H₂, CO and CO₂ is an established technology used mostly for producing hydrogen from heavy fuel oils, primarily in locations where natural gas or lighter hydrocarbons, including naptha, were unavailable or were uneconomical as compared with fuel oil or crude oil. This process is carried out by injecting preheated hydrocarbon, oxygen and steam through a specially designed burner into a closed combustion chamber, where partial oxidation of the hydrocarbons with less than stochiometric oxygen for complete combustion occurs at very high temperature (1350°-1600° C.) and pressures up to 150 atm (Kirk and Othmer, Encyclopedia of Chemical Technology 3rd Edn. 1990 vol. 12 p. 952; Ullamann's Encyclopedia of Industrial Chemistry 5th Edn., 1989, vol. 12, p. 204). The main drawbacks of this process are as follows. This process is operated at a very high temperature and very high pressure and there is extensive soot or carbon formation, particularly from heavy hydrocarbons.

Recently, Ashcroft and co-workers (Nature, vol. 344, 1990, p. 319) have reported selective oxidation of methane to synthesis gas (which is mildly exothermic reaction) using lanthanide ruthenium oxide (Ln₂ Ru₂ O₇ where Ln is lanthanide or rare earth element such as Pr, Sm, Eu, Gd, Tb, Dy, Tm, Yb, Lu) catalysts at 777° C., and total gas hourly space velocity of 4×10⁴ h⁻¹ with CH₄ /O₂ mole ratio 2.0 and N₂ /CH₄ mole ratio of 2.0. The catalyst were prepared by conventional solid state reactions between Ln₂ O₃ and RuO₂ in a sealed silica tube. Although, high methane conversions to CO and H₂ have been obtained using these catalysts, the catalyst cost is exorbitantly high because of the use of extremely costly Ru in the catalyst in stochiometric quantities (i.e. Ru/Ln mole ratio=1.0).

A process for the preparation of a novel composite catalyst, containing transitional and alkaline earth metal oxides, represented by the formula: T_(m) AO_(n) wherein T is a transitional element selected from Ni, Co, Pd, Ru, Rh, Ir or the like or a mixture of two or more thereof, m (i.e. T/A mole ratio) is from 0.01 to 100, A is alkaline earth element chosen from Mg, Ca, Ba, Sr or the like or a mixture of two or more thereof, O is oxygen and n is the number of oxygen atoms needed to fulfil the valance requirement of the transitional and alkaline earth elements in the catalyst, useful for oxidative conversion of methane or natural gas to synthesis gas, CO or H₂ in the presence of free oxygen, has been described and claimed in our copending patent application Ser. No. 07/943,183.

The process comprises the following steps: (i) Mixing thoroughly finely ground one or more transitional metal compound represented by the formula: TX_(a) wherein T is transitional element selected from Ni, Co, Pd, Ru, Rh, Ir or the like or a mixture of two or more thereof; X is selected from NO₃, CH₃ COO, OH, O, CO₃, Cl or like and a is number of X required to fulfil the valence requirement of the transitional element in the compound, and one or more finely ground alkaline earth metal compound, represented by the formula: AY_(b) wherein A is alkaline earth element selected from Mg, Ca, Ba, Sr or like or a mixture of two or more thereof, which are catalyst precursors, Y is selected from NO₃, OH, O, CO₃, CH₃ COO or like, and b is number of Y required to fulfil the valence requirement of the alkaline earth element, which are catalyst precursors, with the T/A mole ratio of about 0.01 to 100, with water, just sufficient to make a thick paste, or without water, (ii) heating the mixture of catalyst precursors to dryness at a temperature of about 80°-250° C. in air, (iii) decomposing the dried mass containing catalyst precursors to their oxides at a temperature of about 400°-1200° C. in presence of air or inert gas (viz. N₂, He, Ar or like) or under vacuum for about 0.5-50 h, (iv) powdering the decomposed mass and making by known methods catalyst pellets, extrudes or granules of required size, and (v) calcining the catalyst at a temperature of about 400°-1500° C. in presence of air, inert gas (viz. N₂, He, Ar or like), CO₂, or their mixture or under vacuum for about 1-100 h.

The main advantages of these catalysts over the other catalysts known in the prior art are as follows: (i) the catalysts have very high activity/selectivity and very high productivity for CO and H₂ (or synthesis gas) in the oxidative conversion of methane to synthesis gas. (ii) The catalyst production cost is much lower, (iii) Using these catalysts, the oxidative conversion of methane or natural gas to synthesis gas could be carried out at much lower temperature. (iv) The catalysts show very high activity in the oxidative conversion of methane or natural gas to synthesis gas at very much higher space velocities and hence have much higher productivity for CO and H₂ in the process (v) The catalysts show no loss of catalytic activity/selectivity in the process for a long period.

In view of limitations of the prior art processes used for the production of synthesis gas from methane (or natural gas), it was found desirable, during the course of the investigation leading to the present invention, to develop an improved process, which is not energy intensive (or highly endothermic), uses cheaper catalysts and operates at lower temperatures for the conversion of methane or natural gas to synthesis gas.

The main object of the present invention is to provide an improved process for the production of synthesis gas by oxidative conversion of methane or natural gas in presence of free oxygen using the novel composite catalysts containing transitional and alkaline earth metal oxides, represented by the formula described above, the process for preparation of which is described and claimed in our copending patent application Ser. No. 07/943,183.

The main finding of the present invention is that synthesis gas (i.e. H₂ and CO) can be produced in high yields and with very high production rate by oxidative conversion of methane to synthesis gas, in a mildly exothermic reaction, using the novel composite catalyst containing transitional and alkaline earth metal oxides, prepared by the process described and claimed in our copending patent application Ser. No. 07/943,183. Another important finding of the present invention is that synthesis gas from methane or natural gas can by the process of the present invention at much lower temperatures and at very much higher space velocities than those used in the processes known in the prior art.

Accordingly, the present invention provides a process for the production of synthesis gas by oxidative conversion of methane or natural gas in the presence of free oxygen using the novel composite catalysts containing transitional and alkaline earth metal oxide prepared by the process described and claimed in our copending patent application Ser. No. 07/943,183.

Accordingly, the present invention provides an improved process for production of synthesis gas by oxidative conversion of methane or natural gas which comprises passing continuously a gaseous reactant mixture comprising methane (or natural gas) and oxygen (or air) with or without water vapor over reduced or unreduced composite catalysts containing transitional and alkaline earth metal oxides, represented by the formula: T_(m) AO_(n) wherein T is transitional element selected from Ni, Co, Pd, Ru, Rh, Ir or like or a mixture of two or more thereof, m (i.e. T/A mole ratio) is from 0.01 to 100, A is alkaline earth element chosen from Mg, Ca, Ba, Sr or like or a mixture of two or more thereof, O is oxygen and n is number of oxygen atoms required to fulfil the valence requirement of the transitional and alkaline earth elements in the catalyst, prepared by the process described and claimed in our copending patent application Ser. No. 07/943,183, in a fixed bed reactor at the following process conditions to produce gaseous products comprising carbon monoxide, hydrogen, carbon dioxide and water vapors, and separating the water vapors, unconverted reactants and feed components other than the reactants and carbon dioxide from the product stream by known methods.

The process operating conditions are as follows.

    ______________________________________                                         Pressure   0.5-50 atm.                                                         Reaction   200°-1000° C.                                         temperature                                                                               (preferably 300°-900° C.)                             Gas hourly space                                                                          10.sup.3 -10.sup.8 cm.sup.3.g.sup.-1.h.sup.-1                       velocity   (preferably 2 × 10.sup.4 -2 × 10.sup.6 cm.sup.3                    .g.sup.-1.h.sup.-1)                                                 Concentration of                                                                          10-90 mole %                                                        CH.sub.4 in feed                                                                          (preferably 20-80 mole %)                                           Concentration of                                                                          1-40%                                                               O.sub.2 in feed                                                                           (preferably 10-36 mole %)                                           CH.sub.4 (or natural                                                                      1.5-10                                                              gas)/O.sub.2 mole                                                                         (preferably 1.8-4)                                                  ratio in feed                                                                  Concentration of                                                                          0-60 mole %                                                         N.sub.2 or Ar                                                                  or their mixture                                                               in feed                                                                        Concentration of                                                                          0-65 mole %                                                         water in feed                                                                  H.sub.2 O/CH.sub.4 (or                                                                    0-3.0 (preferably 0-1)                                              natural gas) mole                                                              ratio in feed                                                                  Concentration of                                                                          0-10 mole %                                                         CO.sub.2 in feed                                                               Concentration of                                                                          0-10 mole %                                                         C.sub.2 H.sub.6 in feed                                                        Concentration of                                                                          0-5 mole %                                                          C.sub.3 - and C.sub.4 -                                                        alkanes in feed                                                                ______________________________________                                    

The catalyst may or may not be reduced before the catalytic reaction. The catalyst reduction may be carried out by passing continuously a gaseous mixture comprising hydrogen and inert gas over the catalyst in the fixed bed reactor at the following conditions.

    ______________________________________                                         Catalyst reduction pressure                                                                         1-5 atm.                                                  Catalyst reduction temperature                                                                      300°-700° C.                                Concentration of H.sub.2                                                                            5-90 mole %                                               in reducing gas mixture                                                        Space velocity of reducing                                                                          10.sup.3 -10.sup.5 cm..sup.3 g..sup.-1 h.sup.-1           gas mixture                                                                    Catalysts reduction period                                                                          0.5-20 h                                                  ______________________________________                                    

When the catalyst is not reduced by hydrogen before the catalytic reaction, the reduction of the catalyst can be effected by passing the reaction mixture comprising CH₄ (or natural gas) and oxygen (or air) over the catalyst at temperature in the range of 600°- 900° C. for a period in the range of 0.5-10 h. Unless the catalyst is reduced this way or by hydrogen as described above, the catalytic oxidative conversion of methane to synthesis gas over the catalyst does not occur at lower temperatures (below 600° C.); the catalyst reaction on the unreduced catalyst occurs above 600° C. The unreduced catalyst is reduced during the catalytic reaction above 600° C. and then the process could be operated at lower temperatures.

In the aforementioned process, the products formed are carbon monoxide (CO) and hydrogen (H₂), as major products and water and carbon dioxide (CO₂) as minor products. The gaseous product stream comprises the above mentioned products, unconverted reactants (i.e. methane or natural gas and oxygen) and components of feed other than reactants.

Because of addition of water in the feed, the H₂ /CO mole ratio in the product is increased by the shift reaction: CO+H₂ O⃡H₂ +CO₂, occurring simultaneously with the oxidative conversion of methane (or natural gas) to synthesis gas.

The present invention reveals that methane or natural gas can be converted to CO and H₂ (or synthesis gas) in high yields with very high productivity by the said process described above.

In the said process of the invention, at 300°-900° C., the conversion of methane (or natural gas), as high as 60-100% with 80-100% selectivity for CO and H and productivity of CO and H as high as 10-30 mol. g.⁻¹ h.⁻¹ and 22-51 mol. g.⁻¹ h.⁻¹ respectively, can be achieved.

The present invention is described with respect to the following examples. These are provided for illustrative purpose only and are not to be construed as limitations on the invention.

Definition of Terms used in the Examples

Total conversion of methane (%)=Mole % of methane converted to all the products

Conversion of methane to particular product (%) or yield for a particular product=Mole % of methane converted to the particular product ##EQU1##

Productivity (or space-time-yield) for a particular product is the amount of the product fromed in the process per unit weight of catalyst per unit time.

Gas hourly space velocity (GHSV) is the volume of gaseous reactant mixture (measured at STP) passed over a unit weight of catalyst per hour.

In the conversion of natural gas, the selectivity and conversion data are based on the carbon balance.

In Examples 1-4, the preparation of the composite catalysts, containing transitional and alkaline earth metal oxides, prepared by the process described and claimed in our copending patent application Ser. No. 07/943,183 is given. Whereas in the other Examples, the process for oxidative conversion of methane (or natural gas) to synthesis gas over the composite catalysts, the preparation of which is described in Examples 1-4, is illustrated.

EXAMPLE-1

In this example preparation of NiO--CaO catalyst (with Ni/Ca mole ratio of 3.0) is illustrated.

Finely ground 3.7 g of Ca(OH)₂, finely ground 43.6 g of Ni(NO₃)₂.6H₂ O and 1.0 ml of deionized water are thoroughly mixed and the resulting thick paste is dried in air oven at 120° C. for 15 h. The dried mass is decomposed at 600° C. in air for 4 h. The decomposed mass is then powdered, pressed binder-free at 4 ton pressure and crushed to 20-30 mesh size particles. The catalyst particles are then calcined in air at 930 C. for 4 h to provide the desired NiO--CaO catalyst. The colour of the catalyst was black. The surface area of the catalyst was 2.46 m² g⁻¹.

EXAMPLE-2

This example illustrates the preparation of NiO--CaO catalyst with Ni/Ca mole ratio of 0.5.

Finely ground 18.52 g of Ca(OH)₂, finely ground 36.4 g of nickel nitrate hexahydrate and 30 ml of deionized water are thoroughly mixed and the resulting paste is dried in air oven at 130° C. for 8 h. The dried mass is then decomposed at 605° C. in air for 5 h. The decomposed solid mass is then powdered, pressed binder-free at 4 ton pressure and crushed to particles of 22-30 mesh. The catalyst particles are then calcined in air at 930° C. for 4 h to provide the desired NiO--CaO catalyst. The colour of the catalyst was gray. The surface area of the catalyst was 0.97 m² g⁻¹.

EXAMPLE-3

This example illustrates the preparation of NiO--MgO catalyst with Ni/Mg mole ratio of 1.0.

Finely ground 29.8 g of Ni(NO₃)₂.6H₂ O, finely ground 9.4 g of magnesium carbonate and 15 ml of deionized water are thoroughly mixed and the resulting thick paste is dried in air oven at 120° C. for 4 h. The dried mass is decomposed in air at 590° C. for 4 h. The decomposed mass is then powdered, pressed binder-free at 5 ton pressure and crushed to 22-30 mesh size particles. The catalyst particles are then calcined in air at 910° C. for 5 h to provide the desired NiO--MgO catalyst. The colour of the catalyst was gray. The surface area of the catalyst was 5.31 m² g⁻¹.

EXAMPLE-4

This example illustrates the preparation of CoO--MgO--BaO catalyst (with Co/(Mg+Ba) mole ratio=Mg/Ba mole ratio=1.0).

Finely ground 23.2 g of Ni(NO₃)₂.6H₂ O, finely ground 12.62 g of Ba(OH)₂.8H₂ O, finely ground 3.7 g of magnesium carbonate and 15 ml of deionized water are thoroughly mixed and the resulting mixture is dried in air oven at 122° C. for 6 h. The dried mass is then decomposed at 595° C. in air for 10 h. Decomposed mass is then powdered pressed binder free at 5 ton pressure and crushed to 22-30 mesh size particles. The catalyst particles are then calcined in presence of air at 910° C. for 5 h to provide the desired CoO--MgO--BaO catalyst. The colour of the catalyst was light brown. The surface area of the catalyst was 3.55 m² g⁻¹.

EXAMPLE-5

This example illustrates the process for the oxidative conversion of methane to CO and H₂ (or synthesis gas) using the NiO--CaO (Ni/Ca mole ratio=3.0), catalyst the preparation of which is described in Example-1.

The oxidative conversion of methane to CO and H₂ (i.e. synthesis gas) over the catalyst was carried out in a flow quartz reactor (i.d=5 mm) packed with the catalyst particles (20 mg) using a mixture of pure methane and oxygen as a feed. The reactor temperature was measured by Chromel-Alumel thermocouple located in the catalyst bed. The reactor effluent gases were cooled at about 0° C. to condense the water formed in the reaction using coiled condenser immersed in ice-water slurry and then analysed for CO, CO₂, H₂ and unconverted methane and O₂ by an on-line gas chromatograph using a Spherocarb column. The change in the volumetric flow rate of gases due to the reaction (CH₄ +1/2O₂ ⃡CO+2H₂) was determined by measuring the flow rate of feed and product gases (after removing water) using soap bubble flow-meter. Before carrying out the reaction, the catalyst was pretreated insitu at the calcination temperature of the catalyst in a flow of pure N₂ (50.0 ml. min⁻¹) for 1 h.

The process performance was evaluated at the following reaction conditions.

    ______________________________________                                         Feed composition                                                                            67 mol % methane and 33 mol % O.sub.2                             Space velocity                                                                              516,000 cm.sup.3 · g.sup.-1 · h.sup.-1          Pressure     1.08 atm.                                                         Reaction temperature                                                                        345°-853° C.                                        ______________________________________                                    

The reaction was carried out first at 853° C. and then at the other temperatures.

The results obtained at different reaction temperatures are as follows.

    ______________________________________                                                      Reaction temperature (°C.)                                              853°                                                                         750°                                                                           650°                                                                           550°                                                                         448°                                                                         345°                          ______________________________________                                         Total CH.sub.4 conversion (%)                                                                 85.9   80.2   75.5 70.1 64.7 58.2                               Selectivity for CO (%)                                                                        96.8   95.4   91.4 90.1 85.6 81.0                               Selectivity for H.sub.2 (%)                                                                   97.4   97.4   94.1 92.0 90.0 80.9                               Productivity for CO                                                                           12.9   11.8   10.7  9.8  8.6  7.3                               (mol. g..sup.-1 h..sup.-1)                                                     Productivity for H                                                                            25.8   24.1   21.9 19.9 17.9 14.6                               (mol. g..sup.-1 h..sup.-1)                                                     H.sub.2 /CO mole ratio                                                                        2.01   2.04   2.06 2.04 2.10 2.00                               in the product.                                                                ______________________________________                                    

EXAMPLE-6

This example illustrates the process for the oxidative conversion of methane to CO and H₂ (or synthesis gas) over the NiO--CaO (Ni/Ca mole ratio=3.0) catalyst, the preparation of which is described in Example-1, reduced by hydrogen before the catalytic reaction.

The reaction over the catalyst was carried out in the reactor and by the procedure similar to that described in Example-5 except that the catalyst pretreated insitu was reduced in the flow (60 cm³ min⁻¹) of a mixture of H₂ and N₂ (18% H₂) at 400° C. for a period of 1 h, before carrying out the catalytic reaction. The reaction was carried out at the following conditions.

    ______________________________________                                         Feed composition                                                                               67 mol % CH.sub.4 and 33 mol % O.sub.2                         Gas hourly space velocity                                                                      515,000 cm.sup.3 · g.sup.-1 · h.sup.-1       (GHSV)                                                                         Pressure        1.08 atm.                                                      Reaction temperature                                                                           305°-700° C.                                     ______________________________________                                    

The results obtained are given below.

    ______________________________________                                                        Reaction temperature (°C.)                                              305°                                                                         402°                                                                             501°                                                                            700°                               ______________________________________                                         Total CH.sub.4 conversion (%)                                                                   63.0   62.3     70.0  83.4                                    Selectivity for CO (%)                                                                          80.7   81.6     87.2  92.6                                    Selectivity for H.sub.2 (%)                                                                     80.3   82.4     84.1  92.0                                    H.sub.2 /CO mole ratio in product                                                               1.99   2.02     1.93  1.99                                    ______________________________________                                    

When the catalyst was not reduced, the reaction on the catalyst did not occur at or below 550° C.

EXAMPLE-7

This example illustrates the process for the oxidative conversion of natural gas to CO and H₂ (or synthesis gas) over the reduced NiO--CaO (Ni/Ca mole ratio=3.0) catalyst, the preparation of which is described in Example-1.

The reaction over the catalyst was carried out in the reactor and by the procedure similar to that described in Example-6 except that, instead of methane, natural gas comprising of methane, ethane and C₃ - and C₄ -alkanes, is used in the feed and the catalyst was reduced by H₂ (20% H₂ in N₂) at 500° C. for 1.5 h, at the following process conditions.

    ______________________________________                                         Feed composition                                                                               59.6 mol % CH.sub.4, 6.0 mol % C.sub.2 H.sub.6,                                1.4 mol % C.sub.3 - and C.sub.4 -alkanes,                                      32 mol % O.sub.2, 0.3 mol % CO.sub.2 and                                       0.7 mol % N.sub.2.                                             GHSV            515,000 cm..sup.3 g..sup.-1 h..sup.-1                          Pressure        1.09 atm.                                                      Reaction temperature                                                                           404°, 654° and 851° C.                    ______________________________________                                    

The results obtained at different temperatures are as follows.

    ______________________________________                                                          Reaction temperature (°C.)                                              404°                                                                           654°                                                                           851°                                     ______________________________________                                         Total carbon conversion (%)                                                                       50.7     63.7   78.8                                        Selectivity for CO (%)                                                                            86.2     93.2   98.0                                        Selectivity for H.sub.2 (%)                                                                       84.5     91.6   93.6                                        H.sub.2 /CO mole ratio in products                                                                1.96     1.97   1.91                                        ______________________________________                                    

EXAMPLE-8

This example illustrates the process for the oxidative conversion of methane to synthesis gas using the NiO--MgO catalyst, the preparation of which is described in Example-3, reduced by the reaction mixture itself.

The catalytic process was carried out in the reactor and by the procedure similar to that described in Example-5 except that after the pretreatment of catalyst in N₂, it was reduced by the reaction mixture at 673° C. for 1 h, at the following process conditions before collecting the process data at different temperatures.

    ______________________________________                                         Feed composition                                                                               67 mol % CH.sub.4 and 33 mol % O.sub.2                         GHSV            516,000 cm.sup.3 · g.sup.-1 ·h.sup.-1        Pressure        1.03 atm.                                                      Reaction temperature                                                                           245°-850° C.                                     ______________________________________                                    

The results at different reaction temperatures are as follows.

    ______________________________________                                                         Reaction temperature (°C.)                                              658°                                                                         430°                                                                           300°                                                                           245°                                                                         850°                            ______________________________________                                         Total CH.sub.4 conversion (%)                                                                    78.1   69.1   66.8 60.8 84.1                                 Selectivity for CO (%)                                                                           97.1   86.4   82.4 78.5 95.7                                 Selectivity for H.sub.2 (%)                                                                      99.2   94.4   89.2 89.7 90.1                                 H.sub.2 /CO mole ratio in products                                                               2.16   2.19   2.17 2.27 1.90                                 ______________________________________                                    

When the catalyst was not reduced by the reaction mixture at 673 C., the catalytic reaction did not occur below 600° C.

EXAMPLE 9

This example illustrates the process for oxidative conversion of methane to synthesis gas using CoO-MgO-BaO catalyst, the preparation of which is described in Example-4. The reaction over the catalyst was carried out in the reactor and by the procedure similar to that described in Example-5 at the following process conditions.

    ______________________________________                                         Feed composition                                                                               66 mol % CH.sub.4 and 34 mol % O.sub.2                         GHSV            516,000 cm.sup.3 · g.sup.-1 · h.sup.-1       Pressure        1.10 atm.                                                      Reaction temperature                                                                           365°-855° C.                                     ______________________________________                                    

The reaction was carried out first at 651° C. and then the other temperatures. The results at different temperatures are as follows.

    ______________________________________                                                      Reaction temperature (°C.)                                              855°                                                                           751°                                                                           651°                                                                            454°                                                                         365°                            ______________________________________                                         Total CH.sub.4 conversion (%)                                                                 100.0    92.9   89.9  82.2 76.1                                 Selectivity for CO (%)                                                                        100.0    87.7   85.7  79.0 73.9                                 Selectivity for H.sub.2 (%)                                                                    93.3    88.1   85.9  80.0 80.8                                 H.sub.2 /CO mole ratio                                                                         1.87    2.01   2.01  2.03 2.19                                 ______________________________________                                    

EXAMPLE-10

This example illustrates the process for the oxidative conversion of methane to CO and H₂ (or synthesis gas) using the NiO--CaO (Ni/Ca mole ratio=0.5) catalyst, the preparation of which is given in Example-2, without the catalyst reaction.

The catalytic process was carried out in the reactor and by the procedure similar to that described in Example-5, at the following conditions.

    ______________________________________                                         Feed composition                                                                               66 mol % CH.sub.4 and 34 mol % O.sub.2                         GHSV            609,000 cm.sup.3 · g.sup.-1 h.sup.-1                  Pressure        2.1 atm.                                                       Reaction temperature                                                                           401°-752° C.                                     ______________________________________                                    

The reaction was carried out first at 752° C. and then at the other temperatures.

The results obtained in the process are as follows.

    ______________________________________                                                        Reaction temperature (°C.)                                              752°                                                                            650°                                                                             551°                                    ______________________________________                                         Total CH.sub.4 conversion (%)                                                                   78.3      73.1     63.8                                       Selectivity for CO (%)                                                                          94.2      90.4     86.1                                       Selectivity for H.sub.2 (%)                                                                     95.7      91.0     84.3                                       H.sub.2 /CO mole ratio                                                                          2.03      2.01     1.96                                       ______________________________________                                    

EXAMPLE-11

This example illustrates the process for the oxidative conversion of methane to synthesis gas (CO and H₂) using the reduced NiO--CaO (Ni/Ca mole ratio=3.0) catalyst, preparation of which is given in Example-1, at different gas hourly space velocities.

The catalytic process was carried out in the reactor and by the procedure similar to that described in Example-6, at the following conditions.

    ______________________________________                                         Feed composition                                                                               67 mol % CH.sub.4 and 33 mol % O.sub.2                         Pressure        1.1 atm.                                                       Gas hourly space velocity                                                                      5.42 × 10.sup.4 -2.15 × 10.sup.6                                   cm.sup.3 · g.sup.-1 · h.sup.-1               Reaction temperature                                                                           500°-751° C.                                     ______________________________________                                    

The results obtained at the different gas hourly space velocities and reaction temperatures are as follows.

    __________________________________________________________________________     Reaction temp. °C.                                                                  655°                                                                          753°                                                                          652°                                                                          751°                                                                          500°                                                                          652°                          GHSV, cm.sup.3 · g.sup.-1 · h.sup.-1                                     5.42 × 10.sup.4                                                                5.42 × 10.sup.4                                                                5.16 × 10.sup.5                                                                5.16 × 10.sup.5                                                                9.7 × 10.sup.5                                                                 2.15 × 10.sup.6                __________________________________________________________________________     Total CH.sub.4                                                                             54.7  67.4   76.0  80.1  60.1  52.4                                conversion (%)                                                                 Selectivity for                                                                            74.8  90.2   91.5  95.3  86.8  88.6                                CO (%)                                                                         Selectivity for                                                                            84.4  90.1   94.0  96.4  80.9  75.8                                H.sub.2 (%)                                                                    H.sub.2 /CO mole ratio                                                                     2.26  2.00   2.06  2.02  1.86  1.71                                Productivity for                                                                           0.66  0.99  10.73 11.78 15.14 29.86                                CO (mol · g.sup.-1 · h.sup.-1)                               Productivity for                                                                           1.50  1.98  22.11 23.86 28.15 51.05                                H.sub.2 (mol · g.sup.-1 · h.sup.-1)                          __________________________________________________________________________

EXAMPLE-12

This example illustrates the process for the oxidative conversion of methane to synthesis gas (CO and H₂) using the reduced NiO--CaO (Ni/Ca mole ratio=3.0) catalyst, the preparation of which is given in Example-1, at different CH₄ /O₂ mole ratios in the feed.

The catalytic process was carried out in the reactor and by the procedure similar to that described in Example-6, using a mixture of pure methane and O₂ as feed at the following reaction conditions.

    ______________________________________                                         CH.sub.4 /O.sub.2 mole ratio in feed                                                              2-4                                                         Pressure           1.15 atm.                                                   Gas hourly space velocity                                                                         516,000 cm.sup.3 · g.sup.-1 ·                                h.sup.-1                                                    Reaction temperature                                                                              500°-607° C.                                  ______________________________________                                    

The results obtained at the different CH/O mole ratios in feed and reaction temperatures are given below.

    ______________________________________                                         Reaction temp. °C.                                                                     501°                                                                           607°                                                                           601°                                                                         502°                                                                         606°                                                                         502°                        CH.sub.4 /O.sub.2 mole ratio                                                                  2.0    2.0    3.0  3.0  4.0  4.0                                ______________________________________                                         Total CH.sub.4 conversion (%)                                                                 65.0   72.4   51.7 47.7 36.0 28.3                               Selectivity for CO (%)                                                                        85.3   90.2   87.2 82.0 90.2 72.9                               Selectivity for H.sub.2 (%)                                                                   84.5   86.4   86.5 78.3 91.4 79.3                               H.sub.2 /CO mole ratio                                                                        1.98   1.92   1.98 1.91 2.03 2.18                               ______________________________________                                    

EXAMPLE-13

This example illustrates the process for the oxidative conversion of methane to synthesis gas (CO and H₂) using the reduced NiO--CaO (Ni/Ca mole ratio=3.0) catalyst, the preparation of which is given in Example-1, at different H₂ O/CH₄ mole ratio in the feed.

The catalytic process was carried out in the reactor and by the procedure similar to that described in Example-6, using a mixture of pure CH₄,O₂ and water vapours as a feed at the following reaction conditions.

    ______________________________________                                         CH.sub.4 /O.sub.2 mole ratio in feed                                                              2.0                                                         H.sub.2 O/CH.sub.4 mole ratio in feed                                                             0 1.0                                                       Pressure           1.2 atm.                                                    Gas hourly space velocity                                                                         520,500 cm.sup.3 · g.sup.-1  ·                               h.sup.-1                                                    Reaction temperature                                                                              409°-851° C.                                  ______________________________________                                    

The results obtained at different H₂ O/CH₄ mole ratios in feed and reaction temperatures are given below.

    ______________________________________                                         Reaction temp. °C.                                                                     650°                                                                           655°                                                                           752°                                                                         646°                                                                         755°                                                                         851°                        H.sub.2 O/CH.sub.4 mole ratio                                                                 0.0    0.1    0.1  1.0  1.0  1.0                                ______________________________________                                         Total CH.sub.4 conversion (%)                                                                 76.1   67.6   77.3 54.4 62.1 69.8                               Selectivity for CO (%)                                                                        92.6   86.7   91.5 45.9 53.2 64.4                               Selectivity for H.sub.2 (%)                                                                   94.2   91.5   92.5 83.9 85.6 94.4                               H.sub.2 /CO mole ratio                                                                        2.04   2.11   2.02 3.66 3.22 2.93                               ______________________________________                                    

The main advantages of the invention are

(i) The process of the present invention involves oxidative conversion of methane (or natural gas) to synthesis gas, which is mildly exothermic reaction, and hence the process is not energy intensive.

(ii) The process of the present invention uses novel composite catalyst containing transitional (preferably Ni or Co) and alkaline earth metal oxides, which is much cheaper than the catalyst containing costly noble metal like ruthenium in stochiometric quantities with other elements, used in the prior art.

(iii) The novel composite catalysts used in the process of present invention show very high activity/selectivity, very high productivity for hydrogen and carbon monoxide and long life in the oxidative conversion of methane (or natural gas) to synthesis gas.

(iv) Synthesis gas could be produced by the process of the present invention in high yields with very high production rate at much lower temperatures than that used in the different processes known in the prior art.

(v) The process of the present invention is operated at much higher space velocities that that used in the different processes known in the prior art.

(vi) In the process of the present invention the H₂ /CO mole ratio in the product gas is about 2.0 and if required can be increased above 2.0 by adding water vapours in the feed. 

We claim:
 1. A process for the production of synthesis gas consisting of a mixture of carbon monoxide and hydrogen by oxidative conversion of methane or natural gas, the process comprising1) passing continuously a gaseous reaction mixture comprising the methane or natural gas and oxygen, with or without water vapors, over a composite catalyst containing transition and alkaline earth metal oxides in a fixed bed reactor at a pressure in the range of 0.5-50 atm, a temperature in the range of 300°-900° C., a gas hourly space velocity in the range of 10³ -10⁸ cm³ . g.⁻¹ h.⁻¹, a CH₄ or natural gas/O₂ mole ratio in the range of 1.8 to 4, and a H₂ O/CH₄ or natural gas mole ratio in the range of 0-3.0, whereby to produce gaseous products containing synthesis gas; said composite catalyst being represented by the formula T_(m) AO_(n), wherein T is a transition element selected from the group consisting of Ni, Co, Pd, Ru, Rh, Ir and mixtures thereof, wherein m is a mole ratio of T/A and is from 0.01 to 100, wherein A is an alkaline earth element selected from the group consisting of Mg, Ca, Ba, Sr and mixtures thereof, wherein O is oxygen and n is a number of oxygen atoms required to fulfil the valence requirement of the transition and alkaline earth elements in the catalyst, and wherein the composite catalyst is prepared by (i) mixing thoroughly catalyst precursors consisting essentially of: a) one or more finely ground transitional metal compounds represented by the formula TX_(a) ; wherein T is the transitional element; wherein X is selected from the group consisting of NO₃, CH₃ COO, OH, O, CO₃ and Cl; and wherein a is a number of X required to complete the valence requirement of the transitional element; and b) one or more finely ground alkaline earth metal compounds represented by the formula AY_(b) ; wherein A is the alkaline earth element; wherein Y is selected from the group consisting of NO₃, OH, O, CO₃ and CH₃ COO; and wherein b is a number of Y required to complete the valence requirement of the alkaline earth element; said catalyst precursors having a T/A mole ratio of about 0.01 to about 100; ii) heating the mixture of catalyst precursors to dryness at a temperature of about 80°-250° C. in air to form a dried mass; iii) decomposing the dried mass containing catalyst precursors to their oxides at a temperature of about 400°-1200° C. in the presence of air or inert gas or under vacuum for about 0.5 to 50 h to form a decomposed mass; iv) powdering the decomposed mass and forming catalyst pellets, extrudes or granules therefrom; and v) calcining the catalyst at a temperature of about 400°-1500° C. in the presence of air, inert gas, CO or their mixture or under vacuum for about 1 to 100 h; and 2) separating the synthesis gas from the gaseous products.
 2. An improved process as claimed in claim 1 wherein the pressure employed ranges from about 1 to 5 atm.
 3. An improved process as claimed in claim 1 wherein the reaction temperature ranges from about 300° to 900° C.
 4. An improved process as claimed in claim 1 wherein the gas hourly space velocity ranges from 2×10⁴ to 2×10⁶ cm³.g⁻¹.h⁻¹.
 5. An improved process as claimed in claim 1 wherein the concentration of methane in feed ranges from 20 to 80 mole %.
 6. An improved process as claimed in claim 1 wherein the concentration of oxygen in feed ranges from 10 to 36 mole %.
 7. An improved process as claimed in claim 1 wherein the concentration of water in the feed ranges from 0 to 65 mole %.
 8. An improved process as claimed in claim 1 wherein the concentration of N₂, Ar or their mixture in the feed ranges from 0 to 60 mole %.
 9. An improved process as claimed in claim 1 wherein the concentration of ethane in the feed ranges from 0 to 10 mole %.
 10. An improved process as claimed in claim 1 wherein the concentration of C₃ - and C₄ -alkanes in the feed ranges from 0 to 5 mole %.
 11. An improved process as claimed in claim 1 wherein the concentration of CO₂ in the feed ranges from 0 to 10 mole %.
 12. An improved process as claimed in claim 1 wherein the H₂ O/CH₄ (or natural gas) mole ratio in the feed ranges from 0 to
 1. 13. An improved process as claimed in claim 1 wherein the catalyst is reduced before the catalytic reaction by passing continuously a gaseous mixture comprising hydrogen and inert gas such as N₂ or Ar with H₂ concentration in the range 5-90 mole % at pressure in the range of 0.5 to 5.0 atm, at temperature in the range of 300° to 700° C., at gas hourly space velocity in the range of 10³ to 10⁵ cm³.g⁻¹.h⁻¹ for a period in the range of 0.5 to 20 h.
 14. An improved process as claimed in claim 13 wherein the catalyst reduction is effected by passing continuously the reaction mixture over the catalyst at temperature in the range of 600° to 900° C. for a period in the range of 0.5 to 10 h.
 15. An improved process as claimed in claim 1 wherein, for the catalyst, the transitional element is chosen from Ni, Co or their mixture, the alkaline earth element is chosen from Mg, Ca, or the like or their mixture and the transitional metal/alkaline earth metal mole ratio is in the range of 0.1 10.0. 